WO2021023135A1 - Feuille d'électrode positive, dispositif de stockage d'énergie électrochimique associé à celle-ci, et appareil - Google Patents

Feuille d'électrode positive, dispositif de stockage d'énergie électrochimique associé à celle-ci, et appareil Download PDF

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WO2021023135A1
WO2021023135A1 PCT/CN2020/106471 CN2020106471W WO2021023135A1 WO 2021023135 A1 WO2021023135 A1 WO 2021023135A1 CN 2020106471 W CN2020106471 W CN 2020106471W WO 2021023135 A1 WO2021023135 A1 WO 2021023135A1
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positive electrode
overcharge
pole piece
conductive material
conductive
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PCT/CN2020/106471
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English (en)
Chinese (zh)
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於洋
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宁德时代新能源科技股份有限公司
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Priority to EP20850999.2A priority Critical patent/EP3905395B1/fr
Publication of WO2021023135A1 publication Critical patent/WO2021023135A1/fr
Priority to US17/511,059 priority patent/US20220109159A1/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H01M4/623—Binders being polymers fluorinated polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/626—Metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/665—Composites
    • H01M4/667—Composites in the form of layers, e.g. coatings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/668—Composites of electroconductive material and synthetic resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • This application relates to the field of electrochemistry, in particular to a positive pole piece and related electrochemical energy storage devices and equipment.
  • Lithium ion secondary batteries mainly rely on the reciprocating movement of lithium ions between the positive electrode active material and the negative electrode active material for charging and discharging.
  • Lithium-ion secondary batteries can provide stable voltage and current during use, and the use process is green and environmentally friendly, so they are widely used in various electrical equipment, such as mobile phones, tablet computers, notebook computers, electric bicycles, electric cars, etc. .
  • the purpose of this application is to provide a positive pole piece and its related electrochemical energy storage device and equipment to solve the problems in the prior art.
  • a positive electrode sheet which includes a positive electrode current collector, a positive electrode active material layer on at least one side of the positive electrode current collector, and a positive electrode active material layer located between the positive electrode active material layer and the positive electrode current collector.
  • the overcharge sensitive substance is a polymer that includes a monosaccharide structural unit and includes at least one of a carbonate group and a phosphate group;
  • the unit of x is nm, and the unit of y is 1.
  • Another aspect of the present application provides an electrochemical energy storage device, including the above-mentioned positive pole piece.
  • the positive pole piece provided in this application can be used to form an electrochemical energy storage device.
  • the electrochemical energy storage device When the electrochemical energy storage device is charged, if overcharge and abuse occur, lower temperature will cause the overcharge sensitive material to undergo chemical reaction and degradation , which in turn causes the physical structure of the material to change, causes the conductive material particles in the safety layer to separate, destroys the conductive network in the safety layer, increases the internal resistance of the electrochemical energy storage device, and blocks the positive electrode current collector and the positive electrode activity
  • the electronic conduction between the material layers cuts off the charging current in time, effectively preventing thermal runaway of the electrochemical energy storage device, avoiding safety problems such as fire and explosion, and improving the overcharge safety performance of the electrochemical energy storage device.
  • the reliability is difficult to guarantee, and there is a potential safety hazard.
  • the safety layer using the overcharge-sensitive material provided in the present application has better reliability, and thus can make the electrochemical energy storage device have better safety.
  • the present application provides a battery module including the above electrochemical energy storage device.
  • the present application provides a battery pack including the above-mentioned battery module.
  • the present application provides a device including the above-mentioned electrochemical energy storage device.
  • the electrochemical energy storage device can be used as a power source for the device or as an energy storage unit of the device.
  • the battery module, battery pack, and equipment of the present application include the electrochemical energy storage device provided in the present application, and thus have at least the same advantages as the electrochemical energy storage device of the present application.
  • FIG. 1 is a schematic diagram of voltage and temperature changes in the overcharge safety performance test of one of the batteries in Embodiment 13 of this application;
  • Figure 2 is a schematic diagram of voltage and temperature changes in the overcharge safety performance test of one of the batteries in Comparative Example 2 of the application;
  • Fig. 3 is a schematic diagram of an embodiment of a secondary battery
  • FIG. 4 is a schematic diagram of an embodiment of a battery module
  • FIG. 5 is a schematic diagram of an embodiment of the battery pack
  • Figure 6 is an exploded view of Figure 5;
  • Fig. 7 is a schematic diagram of an embodiment of a device in which a secondary battery is used as a power source.
  • any lower limit may be combined with any upper limit to form an unspecified range; and any lower limit may be combined with other lower limits to form an unspecified range, and any upper limit may be combined with any other upper limit to form an unspecified range.
  • every point or single value between the end points of the range is included in the range. Therefore, each point or single numerical value can be used as its own lower limit or upper limit, combined with any other point or single numerical value, or combined with other lower or upper limits to form an unspecified range.
  • the first aspect of the application provides a positive electrode sheet, which includes a positive electrode current collector, a positive electrode active material layer on at least one side of the positive electrode current collector, and a safety layer between the positive electrode active material layer and the positive electrode current collector;
  • the positive electrode active material layer includes Positive active material
  • the safety layer includes binding material, conductive material and overcharge sensitive material;
  • the overcharge sensitive substance includes a monosaccharide structural unit, and includes at least one of a carbonate group and a phosphate group;
  • the average particle size x of the conductive material and the weight average molecular weight y of the overcharge sensitive material satisfy formula 1;
  • the unit of x is nm, and the unit of y is 1.
  • the positive pole piece provided in this application can be used to form an electrochemical energy storage device.
  • the overcharge-sensitive material in the safety layer can be under certain conditions (for example, excessive temperature, Voltage and other conditions) chemical reaction occurs, and the carbohydrate unit fragments containing carbonate groups and/or phosphate groups produced by degradation can be quickly miscible in electrolytes containing a large amount of carbonate solvents, changing from large molecular chains that are difficult to move freely into The freely movable small molecule solution or sol state pushes the conductive materials in the security layer to move together, destroying the conductive network in the security layer.
  • the ability of overcharge sensitive materials to promote the disintegration of the conductive network when it breaks and degrades is a protection
  • the inventor of the present application unexpectedly discovered that when the molecular weight of the overcharge sensitive material and the particle size of the conductive material used in the security layer meet a certain matching relationship, the above effect can be well exerted.
  • the average particle size x of the conductive material and the weight average molecular weight y of the overcharge sensitive material may satisfy the relationship of x/y ⁇ 0.25 (the unit of x is nm and the unit of y is 1).
  • the average particle size of the conductive material usually refers to the particle size of the conductive material coated in the security layer, and the average particle size is obtained through the observation of the electron microscope.
  • the average particle size is obtained through the observation of the electron microscope.
  • For non-spherical particles take the major axis diameter and The average value of the minor axis diameter is the average particle diameter.
  • the average particle diameter x of the conductive material and the weight average molecular weight y of the overcharge sensitive material can satisfy 0.001 ⁇ x/y ⁇ 0.25, 0.001 ⁇ x/y ⁇ 0.005, 0.005 ⁇ x/y ⁇ 0.01, 0.01 ⁇ x/y ⁇ 0.05, 0.05 ⁇ x/y ⁇ 0.1, 0.1 ⁇ x/y ⁇ 0.15, 0.15 ⁇ x/y ⁇ 0.2, or 0.2 ⁇ x/y ⁇ 0.25.
  • the conductive material with a smaller average particle size x is more likely to shift and disconnect the conductive network when the overcharge-sensitive material breaks; therefore, for the conductive material itself, it is possible to choose a higher Small particle size.
  • the average particle size x of the conductive material may satisfy: x ⁇ 600nm, x ⁇ 500nm, x ⁇ 400nm, x ⁇ 300nm, x ⁇ 200nm, or x ⁇ 100nm.
  • the overcharge sensitive material with a large weight average molecular weight y can have a stronger driving effect on the disconnection of the conductive network when it is broken; the overcharge sensitive material with too low weight average molecular weight y Substances may result in the inability to stabilize the conductive network during normal use; overcharge-sensitive materials with too high weight average molecular weight y may cause difficulties in chemical reactions of the overcharge-sensitive materials, longer degradation time, and affect response speed.
  • the weight-average molecular weight y of the overcharge sensitive substance may satisfy: 2000 ⁇ y ⁇ 20000, 2000 ⁇ y ⁇ 3000, 3000 ⁇ y ⁇ 4000, 4000 ⁇ y ⁇ 5000, 5000 ⁇ y ⁇ 6000, 6000 ⁇ y ⁇ 8000, 8000 ⁇ y ⁇ 10000, 10000 ⁇ y ⁇ 12000, 12000 ⁇ y ⁇ 14000, 14000 ⁇ y16000, 16000 ⁇ y ⁇ 18000, or 18000 ⁇ y ⁇ 20000.
  • the overcharge-sensitive material may include a monosaccharide structural unit, and may include at least one of a carbonate group and a phosphate group, so that it can be under certain conditions (for example, temperature, Voltage and other conditions), a chemical reaction can take place to degrade substances that produce sugar unit fragments containing carbonate groups and/or phosphate groups.
  • the overcharge sensitive substance may be at least one of sugar carbonate, sugar phosphate, and mixed carbonic acid and phosphoric acid ester of sugar.
  • Sugar carbonates usually refer to esters formed by replacing at least part of the hydroxyl groups in sugar molecules with carbonic acid groups.
  • the molecular structure of sugar carbonates usually includes carbonate groups; sugar phosphates usually refer to sugar molecules.
  • the molecular structure of the sugar phosphate ester usually includes a phosphate group; the carbonic acid and phosphate mixed ester compounds of sugar usually mean that at least part of the hydroxyl groups in the sugar molecule are The ester compound formed by the substitution of carbonic acid group and phosphoric acid group.
  • the molecular structure of the mixed ester of carbonic acid and phosphoric acid of sugar usually includes a carbonate group and a phosphate group.
  • carbonic acid groups and/or phosphate groups can be used as crosslinking groups to connect multiple monosaccharide molecules and/or polysaccharide molecules (for example, they can be linked to multiple hydroxyl groups belonging to different sugar molecules).
  • the reaction generates carbonate groups or phosphate groups) to form part of the bulk phase space structure. It can also expose part of the outer ends of unsubstituted carbonic acid and/or phosphoric acid, and optionally alkyl groups (for example, chain C1-C5 alkyl group) for end-capping, which can better stabilize the conductive network in the security layer during normal use, and produce more obvious structural changes when degradation occurs, and improve the response to overcharge speed.
  • alkyl groups for example, chain C1-C5 alkyl group
  • the degree of crosslinking of the overcharge-sensitive substance is usually based on the ability to normally prepare the overcharge prevention layer, which should be known to those skilled in the art.
  • monosaccharide structural units can also provide sites for the carbonate and phosphate esterification of sugar molecules; carbonate and phosphate groups have a good affinity with common electrolytes, and have great affinity for Li + Good coordination.
  • the small molecular sugar units and carbonate or phosphate fragments produced by the cleavage can be quickly miscible in electrolytes containing a large amount of carbonate solvents, improving the response speed of the anti-overcharge effect.
  • the overcharge sensitive substance may be an esterified product formed by monosaccharides, polysaccharides (including oligosaccharides), or a mixture of monosaccharides and polysaccharides.
  • Monosaccharides usually refer to a type of sugar that cannot be further hydrolyzed.
  • the molecular structure of monosaccharides can usually include 3-6 carbon atoms; polysaccharides usually refer to two or more monosaccharide units (for example, 2-10, 2, 3). 1, 4, 5, 6, 7, 8, 9, 10, or more than 10 monosaccharide units) sugar chains formed by the combination of glycosidic bonds.
  • the polysaccharide can be selected as an oligosaccharide containing 2-10 monosaccharide structural units to ensure that the overcharge sensitive substance has a suitable weight average molecular weight.
  • the overcharge sensitive material may be a carbonate of sugar. Compared with other materials (for example, phosphate), the carbonate has better compatibility with the electrolyte. .
  • the overcharge sensitive substance may be one or a combination of one or more of monosaccharide carbonate, polysaccharide carbonate, monosaccharide and polysaccharide mixture carbonate, and the like.
  • the conductive material in the safety layer can generally ensure that the safety layer has a certain conductive effect, and when the overcharge sensitive material degrades, it can be produced containing carbonate groups and/or phosphate groups.
  • the sugar unit fragments of the cluster are pushed and displaced, resulting in the destruction of the conductive network in the security layer;
  • the conductive material in the security layer may include one or more of metal conductive materials, carbon-based conductive materials, and polymer conductive materials. .
  • the metal material can be selected from aluminum, aluminum alloy, copper, copper alloy, nickel, nickel alloy, and titanium.
  • the carbon-based conductive material may be selected from Ketjen black, mesophase carbon microspheres, activated carbon, graphite, conductive carbon black, acetylene black, carbon fiber, carbon nanotube, One or more combinations of graphene, etc., for example, the polymer conductive material can be selected from polysulfur nitrides, aliphatic conjugated polymers, aromatic ring conjugated polymers, aromatic heterocyclic conjugated polymers A combination of one or more of them.
  • the conductive material may be a carbon-based conductive material. Because of its lower density and higher conductivity, it can be added in a small amount to satisfy the safety layer in the normal use of electrochemical energy storage. When the device is electrically conductive, it is easy to move when the overcharge sensitive material is degraded, destroying the conductive network, and improving the reliability of overcharge prevention.
  • the conductive material is a zero-dimensional carbon-based conductive material to reduce the random bridging effect of the conductive material in response to overcharge prevention.
  • the conductive material may be zero-dimensional conductive carbon black, which has good conductivity and is easy to achieve a small particle size.
  • the overcharge-sensitive substance can undergo a chemical reaction under certain conditions (for example, temperature, voltage, etc.) to degrade to produce sugar unit fragments containing carbonate groups and/or phosphate groups Of the substance.
  • the conditions for degradation of the overcharge-sensitive material usually correspond to the overcharge condition of the positive pole piece or electrochemical energy storage device.
  • the specific The conditions for overcharging can be changed.
  • the degradation conditions of overcharge-sensitive materials have a certain relationship with temperature and overcharge voltage. For example, when the positive pole piece is used at a high temperature, the overcharge-sensitive materials will reach a lower overcharge voltage.
  • Degradation occurs to ensure the safe use of the electrochemical energy storage device; for another example, if the positive pole piece is overcharged when its own use temperature is low, the overcharge-sensitive material can reach a relatively high overcharge voltage, and part of it It begins to degrade after heating up, but the overall temperature of the positive pole piece is much lower than that of the positive pole piece using traditional PTC materials.
  • the specific degradation voltage and temperature of overcharge sensitive substances can be adjusted according to actual needs.
  • the positive pole piece degrades the overcharge-sensitive material under the condition that the charging voltage is ⁇ V and the temperature is ⁇ °C, where 4.2 ⁇ 5.5, 4.2 ⁇ 4.5, 4.5 ⁇ ⁇ 4.8, 4.8 ⁇ 5.2, or 5.2 ⁇ 5.5, 35 ⁇ 80, 35 ⁇ 40, 40 ⁇ 45, 45 ⁇ 50, 50 ⁇ 55, 55 ⁇ 60, 60 ⁇ 65, 65 ⁇ 70, 70 ⁇ 75, or 75 ⁇ 80.
  • the positive pole pieces within the above ⁇ and ⁇ range can not only ensure normal use under normal voltage and temperature, but also ensure the reliability of overcharge safety performance.
  • the binding material in the safety layer is usually used to ensure that the safety layer is tightly connected with the current collector and the positive electrode active material layer.
  • the binding material can generally be various binders suitable for preparing positive electrode plates in the field.
  • the binding material can be selected from polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, polyurethane, polyacrylonitrile, One of polyimide, epoxy resin, silicone resin, ethylene-vinyl acetate copolymer, styrene butadiene rubber, styrene-acrylic rubber, polyacrylic acid, polyacrylic acid-acrylate copolymer and polyethylene-acrylate copolymer, etc.
  • the binding material is selected from one or a combination of polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, and the like.
  • the bonding substance in the security layer usually needs to have a certain proportion to ensure the normal use of the security layer. However, an excessively high proportion of the binding material may hinder the disintegration of the conductive network when the overcharge sensitive material is degraded.
  • the mass of the bonding substance accounts for 30% to 60%, 30% to 35%, 35% to 40%, 40% to 45%, 45% to 50% of the total mass of the safety layer. %, 50% to 55%, or 55% to 60%.
  • the content of the overcharge sensitive substance and the conductive substance in the safety layer usually needs to have a certain matching to ensure the conductivity of the safety layer during normal use and the blocking ability when overcharge occurs. Too little overcharge sensitive material or too large ratio to conductive material may cause its degradation and still cannot effectively promote the disconnection of the conductive network.
  • the positive pole piece provided in the present application when the mass ratio of the overcharge sensitive substance to the conductive substance in the safety layer is not less than 2:1, the positive pole piece can better exert the anti-overcharge effect. When the overcharge-sensitive material that meets this ratio degrades and breaks, it can quickly promote the displacement of the conductive material and destroy the conductive network.
  • the mass ratio of the overcharge sensitive material to the conductive material in the security layer may be ⁇ 2, ⁇ 3, ⁇ 4, or ⁇ 5.
  • the content of overcharge-sensitive substances and conductive substances in the security layer is within a specific range, which can better ensure the conductive effect of the security layer during normal use.
  • the mass of the overcharge sensitive material accounts for 30%-50%, 30%-35%, 35%-40%, 40%-45%, or 45%-50% of the total mass of the safety layer. %.
  • the mass of the conductive material accounts for 6% to 18%, 6% to 8%, 8% to 10%, 10% to 12%, 12% to 14% of the total mass of the safety layer. 14%-16%, or 16%-18%.
  • the positive electrode current collector is coated with a positive electrode active material layer.
  • one surface or both surfaces of the positive electrode current collector may be coated with the positive electrode active material layer.
  • the safety layer is provided between the positive electrode current collector and the positive electrode active material layer, the number of safety layers and the number of positive electrode active material layers are generally the same. That is, if the positive electrode active material layer is coated on one surface of the positive electrode current collector, it has one safety layer; if the positive electrode active material layer is coated on both surfaces of the positive electrode current collector, it has two safety layers.
  • the positive electrode current collector can usually be a layered body.
  • the positive electrode current collector is provided with a positive electrode active material layer on one surface, or can be provided with a positive electrode active material layer on both surfaces, and at least one of the positive electrode active material layer and the positive electrode A safety layer is provided between the current collectors.
  • the positive current collector is usually a structure or part that can collect current.
  • the positive electrode current collector can be various materials in the field that are suitable for use as the positive electrode current collector of the positive pole piece in the electrochemical energy storage device.
  • the positive electrode current collector can include but not limited to metal foil, etc., more specifically, it can include but not Limited to copper foil, aluminum foil, etc.
  • the positive electrode active material can generally be various materials in the field suitable for the positive electrode active material of the positive electrode sheet in the electrochemical energy storage device.
  • the positive electrode active material can include lithium manganese oxide.
  • Compounds such as lithium manganese oxide compounds may include, but are not limited to, one or a combination of lithium manganese oxide, lithium nickel manganese oxide, lithium nickel cobalt manganese oxide, and the like.
  • the positive electrode active material can also include various other materials suitable for the positive electrode active material of the positive electrode sheet in the electrochemical energy storage device, for example, it can also include but not limited to lithium cobaltate, lithium iron phosphate, lithium iron phosphate, etc. One or more of them.
  • the positive active material layer may also generally include a binder, a conductive agent, etc.
  • the binder and conductive agent suitable for preparing the positive active material layer of an electrochemical energy storage device should be known to those skilled in the art.
  • the binder in the positive active material layer may be styrene butadiene rubber (SBR), water-based acrylic resin, sodium carboxymethyl cellulose (CMC), polyvinylidene fluoride (PVDF), poly One or more combinations of tetrafluoroethylene (PTFE), ethylene-vinyl acetate copolymer (EVA), polyvinyl alcohol (PVA), and polyvinyl butyral (PVB).
  • SBR styrene butadiene rubber
  • CMC sodium carboxymethyl cellulose
  • PVDF polyvinylidene fluoride
  • PTFE ethylene-vinyl acetate copolymer
  • EVA polyvinyl alcohol
  • PVB polyvinyl butyral
  • the conductive agent in the positive electrode active material can be one or more of graphite, superconducting carbon, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, graphene, and carbon nanofibers. combination.
  • the positive electrode active material layer may generally include a positive electrode active material, a binder, a conductive agent, etc.
  • the preparation method of the positive pole piece may specifically include the following steps: After the conductive material and the overcharge-sensitive material form a slurry, they are coated on the positive electrode current collector to provide a positive electrode current collector with a safety layer; the positive electrode active material, binder, and conductive agent are mixed to form a slurry, and then coated On the security layer.
  • the second aspect of the present application provides an electrochemical energy storage device, including the positive pole piece provided in the first aspect of the present application.
  • the electrochemical energy storage device provided in this application may be a super capacitor, a lithium ion battery, a lithium metal battery, or a sodium ion battery.
  • the electrochemical energy storage device is a lithium ion battery is shown, but the present application is not limited thereto.
  • the electrochemical energy storage device may be a lithium-ion battery.
  • the lithium-ion battery it may include a positive pole piece, a negative pole piece, and a separator between the positive pole piece and the negative pole piece. , Electrolyte.
  • the positive pole piece may be the positive pole piece provided in the first aspect of the present application.
  • the method for preparing lithium ion batteries should be known to those skilled in the art.
  • each of the positive pole piece, the separator and the negative pole piece can be a layered body, which can be cut to a target size and stacked one after another. It can be wound to a target size to form a battery cell, and can be further combined with an electrolyte to form a lithium ion battery.
  • the negative electrode sheet usually includes a negative electrode current collector and a negative electrode active material layer on the surface of the negative electrode current collector, and the negative electrode active material layer usually includes a negative electrode active material.
  • the negative electrode current collector can generally be a layered body.
  • the negative electrode current collector is provided with a negative electrode active material layer on one surface, or can be provided with a negative electrode active material layer on both surfaces.
  • the negative electrode current collector is usually a structure or part that collects current.
  • the negative electrode current collector can be various materials suitable for use as the negative electrode current collector of a lithium ion battery in the field.
  • the negative electrode current collector can include but is not limited to metal foil, etc., more specifically It can include but not limited to copper foil.
  • the negative active material in the negative active material layer can be various materials suitable for the negative active material of lithium ion batteries in the field, for example, it can include but not limited to graphite, soft carbon, hard carbon, carbon fiber , Mesophase carbon microspheres, silicon-based materials, tin-based materials, lithium titanate or other metals that can form alloys with lithium, or a combination of one or more of them.
  • graphite can be selected from one or a combination of artificial graphite, natural graphite and modified graphite
  • silicon-based material can be selected from one of elemental silicon, silicon-oxygen compounds, silicon-carbon composites, and silicon alloys.
  • tin-based materials can be selected from one or more combinations of elemental tin, tin oxide compounds, tin alloys, and the like.
  • the negative active material layer may also generally include a binder, a conductive agent, etc.
  • the binder and conductive agent suitable for preparing the negative active material layer of an electrochemical energy storage device should be known to those skilled in the art.
  • the binder in the negative active material layer may be styrene butadiene rubber (SBR), water-based acrylic resin, sodium carboxymethyl cellulose (CMC), polyvinylidene fluoride (PVDF), poly One or more combinations of tetrafluoroethylene (PTFE), ethylene-vinyl acetate copolymer (EVA), polyvinyl alcohol (PVA), and polyvinyl butyral (PVB).
  • the conductive agent in the negative electrode active material can be one or more of graphite, superconducting carbon, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, graphene, and carbon nanofibers. combination.
  • the separator can be various materials suitable for lithium ion battery separators in the field, for example, it can include but not limited to polyethylene, polypropylene, polyvinylidene fluoride, aramid, and polyterephthalene.
  • polyethylene polypropylene
  • polyvinylidene fluoride polyvinylidene fluoride
  • aramid polyvinylidene fluoride
  • polyterephthalene One or a combination of ethylene glycol formate, polytetrafluoroethylene, polyacrylonitrile, polyimide, polyamide, polyester, and natural fibers.
  • the electrolyte can be various electrolytes suitable for lithium-ion batteries in the art.
  • the electrolyte usually includes an electrolyte and a solvent, and the electrolyte usually includes a lithium salt.
  • the lithium salt can be an inorganic Lithium salt and/or organic lithium salt, etc., specifically including but not limited to, lithium salt may be selected from LiPF 6 , LiBF 4 , LiN(SO 2 F) 2 (abbreviated as LiFSI), LiN(CF 3 SO 2 ) 2 (Abbreviated as LiTFSI), LiClO 4 , LiAsF 6 , LiB(C 2 O 4 ) 2 (abbreviated as LiBOB), LiBF 2 C 2 O 4 (abbreviated as LiDFOB), one or more combinations.
  • the concentration of the electrolyte may be between 0.8 mol/L and 1.5 mol/L.
  • the solvent can be various solvents suitable for the electrolyte of lithium-ion batteries in the art.
  • the solvent of the electrolyte is usually a non-aqueous solvent, which can be an organic solvent. Specifically, it can include but not limited to ethylene carbonate, propylene carbonate, and carbonic acid. One or more combinations of butene ester, pentene carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, ethyl methyl carbonate, etc. or their halogenated derivatives.
  • the electrochemical energy storage device is a secondary battery.
  • the present application has no particular limitation on the shape of the secondary battery, which may be cylindrical, square or other arbitrary shapes.
  • Fig. 3 shows a secondary battery 5 with a square structure as an example.
  • the secondary battery can be assembled into a battery module, and the number of secondary batteries contained in the battery module can be multiple, and the specific number can be adjusted according to the application and capacity of the battery module.
  • Fig. 4 is a battery module 4 as an example.
  • a plurality of secondary batteries 5 may be arranged in sequence along the length direction of the battery module 4. Of course, it can also be arranged in any other manner. Furthermore, the plurality of secondary batteries 5 can be fixed by fasteners.
  • the battery module 4 may further include a housing having an accommodation space, and a plurality of secondary batteries 5 are accommodated in the accommodation space.
  • the above-mentioned battery modules can also be assembled into a battery pack, and the number of battery modules contained in the battery pack can be adjusted according to the application and capacity of the battery pack.
  • FIGS 5 and 6 show the battery pack 1 as an example.
  • the battery pack 1 may include a battery box and a plurality of battery modules 4 disposed in the battery box.
  • the battery box includes an upper box body 2 and a lower box body 3.
  • the upper box body 2 can be covered on the lower box body 3 and forms a closed space for accommodating the battery module 4.
  • Multiple battery modules 4 can be arranged in the battery box in any manner.
  • the device includes the above-mentioned secondary battery.
  • the secondary battery can be used as a power source for the device or as an energy storage unit of the device.
  • the device can be, but is not limited to, mobile devices (such as mobile phones, laptop computers, etc.), electric vehicles (such as pure electric vehicles, hybrid electric vehicles, plug-in hybrid electric vehicles, electric bicycles, electric scooters, electric golf Vehicles, electric trucks, etc.), electric trains, ships and satellites, energy storage systems, etc.
  • the device can select a secondary battery (Cell), a battery module (Module) or a battery pack (pack) according to its usage requirements.
  • Cell secondary battery
  • Mode battery module
  • pack battery pack
  • Figure 7 is a device as an example.
  • the equipment is a pure electric vehicle, a hybrid electric vehicle, or a plug-in hybrid electric vehicle.
  • battery packs or battery modules can be used.
  • the device may be a mobile phone, a tablet computer, a notebook computer, etc.
  • the device is usually thin and light, and can use secondary batteries as a power source.
  • the "sucrose carbonate" of Example 10 has a hydroxyl esterification degree of 0.88;
  • the "carbonic acid and phosphoric acid mixed esterification of sucrose" of Example 12 is firstly carbonated to a weight average molecular weight of 3000-4000, and an esterification degree of 0.6, and then phosphoric acid is esterified to an esterification degree of 0.9;
  • the raw material degraded cellulose has a weight average molecular weight of 1300, is carbonated to a hydroxyl esterification degree of 0.85, and is fully capped with methyl;
  • the "degradable chitosan carbonate" raw material of Example 16 degrades chitosan with a weight average molecular weight of 4000-5000, is carbonated to a hydroxyl esterification degree of 0.85, and is fully capped with methyl;
  • a uniform , Dense security layer in which the thickness of the metal conductive layer aluminum foil is 12 ⁇ m, the thickness of the security layer when coated on one side is 3 ⁇ m, and the thickness of the security layer when coated on both sides is 1.5 ⁇ m.
  • Ethylene carbonate (EC), propylene carbonate (PC) and dimethyl carbonate (DMC) are mixed uniformly in a weight ratio of 1:1:1 to obtain an organic solvent; then lithium salt LiPF 6 is dissolved in the above organic solvent , Mix well to obtain an electrolyte, in which the concentration of LiPF 6 is 1 mol/L.
  • the positive pole piece, the polyethylene porous separation film, and the negative pole piece are laminated in order, and then wound to obtain a battery; the battery is placed in an outer package, electrolyte is injected and packaged to obtain a lithium ion secondary battery.
  • the preparation method of Comparative Example 1 refers to Example 7.
  • Comparative Example 2 refers to Example 1. The difference is that the safety layer is not prepared at all in Comparative Example 2, and the active material layers are directly prepared on the two surfaces of the current collector.
  • the preparation method of Comparative Example 3 refers to Example 1. The difference is that no overcharge sensitive substance is added to the prepared security layer slurry, and the use ratio of the adhesive substance is 90%, and the use ratio of the conductive substance is 10%.
  • Comparative Example 4 refers to Example 28. The difference is that in the prepared safety layer slurry, degraded cellulose with a weight average molecular weight of 10,000 is used instead of the overcharge sensitive substance.
  • FIG. 1 shows a schematic diagram of voltage and temperature changes in the overcharge safety performance test of one of the batteries in Example 13
  • FIG. 2 shows a schematic diagram of voltage and temperature changes in the overcharge safety performance test of one of the batteries in Comparative Example 2.
  • Cycle capacity retention rate (%) discharge capacity at the 100th cycle/discharge capacity at the first cycle ⁇ 100%
  • Example 1 6/6 94.3%
  • Example 2 4/6 94.1%
  • Example 3 6/6 94.2%
  • Example 4 3/6 94.0%
  • Example 5 2/6 94.1%
  • Example 6 4/6 94.0%
  • Example 7 3/6 93.7%
  • Example 8 6/6 94.4%
  • Example 9 4/6 94.2%
  • Example 10 6/6 93.9%
  • Example 11 2/6 93.9%
  • Example 12 4/6 94.1%
  • Example 13 6/6 94.2%
  • Example 14 6/6 94.0%
  • Example 15 6/6 94.1%
  • Example 16 6/6 94.3%
  • Example 17 3/6 94.3%
  • Example 18 6/6 94.1%
  • Example 19 6/6 94.2%
  • Example 20 6/6 94.0%
  • Example 21 6/6 92.6%
  • Example 22 6/6 94.1%
  • Example 23 6/6 94.4%
  • Example 24 2/6 93.9%
  • Example 25 3/6 94.3%
  • Example 26 3/6 94.1%
  • Example 27 5/6 94.0%
  • Example 28 6/6 94.0% Comparative example 1 0/6 93.9% Comparative example 2 0/6 92.9% Comparative example 3 0/6 93.8% Comparative example 4 0/6 93.5%
  • Comparative Example 4 show that the use of polysaccharides without carbonic acid groups or phosphoric acid groups to replace the overcharge-sensitive substances in this application can not achieve the effect of preventing overcharge.
  • this application effectively overcomes various shortcomings in the prior art and has a high industrial value.

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  • Chemical & Material Sciences (AREA)
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  • Electrochemistry (AREA)
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  • Engineering & Computer Science (AREA)
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Abstract

La présente invention se rapporte au domaine de l'électrochimie, et concerne en particulier une feuille d'électrode positive, un dispositif de stockage d'énergie électrochimique associé à celle-ci, et un appareil. La feuille d'électrode positive de la présente invention comprend un collecteur de courant positif, une couche de matériau actif positif située sur au moins une surface du collecteur de courant positif, et une couche de sécurité située entre la couche de matériau actif positif et le collecteur de courant positif. La couche de matériau actif positif comprend un matériau actif positif. La couche de sécurité comprend un matériau adhésif, un matériau conducteur et un matériau sensible à la surcharge. Le matériau sensible à la surcharge comprend des unités structurales de monosaccharide et un polymère d'au moins un groupe fonctionnel ester carbonique ou un groupe fonctionnel ester de phosphate. Un diamètre de particule moyen x du matériau conducteur et un poids moléculaire moyen en poids y du matériau sensible à la surcharge satisfont la formule 1. La couche de sécurité de la présente invention utilise le matériau sensible à la surcharge pour obtenir une fiabilité supérieure, ce qui permet d'améliorer la sécurité des dispositifs de stockage d'énergie électrochimique.
PCT/CN2020/106471 2019-08-08 2020-07-31 Feuille d'électrode positive, dispositif de stockage d'énergie électrochimique associé à celle-ci, et appareil WO2021023135A1 (fr)

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EP20850999.2A EP3905395B1 (fr) 2020-07-31 Plaque d'électrode positive et appareil et dispositif de stockage d'énergie électrochimique associés
US17/511,059 US20220109159A1 (en) 2019-08-08 2021-10-26 Positive electrode plate and related electrochemical energy storage apparatus and device

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CN110400933B (zh) * 2019-08-08 2020-12-04 宁德时代新能源科技股份有限公司 正极极片及包括该正极极片的电化学装置
CN110429240B (zh) 2019-08-08 2020-12-04 宁德时代新能源科技股份有限公司 正极极片及包括该正极极片的电化学装置
CN113764612B (zh) * 2020-05-29 2023-10-13 珠海冠宇电池股份有限公司 一种含有高安全性热敏涂层的正极极片及锂离子电池
US11502300B1 (en) 2021-10-13 2022-11-15 Shenzhen Capchem Technology Co., Ltd. Secondary battery
CN113644275B (zh) * 2021-10-13 2022-02-22 深圳新宙邦科技股份有限公司 一种二次电池
CN114759161A (zh) * 2022-05-12 2022-07-15 北京卫蓝新能源科技有限公司 一种多层正极片及其制备方法
CN115084440B (zh) * 2022-06-30 2024-01-16 蜂巢能源科技股份有限公司 一种低阻抗正极极片及其制备方法和应用

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